Herbicidal hexachloroacetone-oil mixture and stabilization thereof



Unite The present invention relates to the stabilization of hexachloroacetone-oil mixtures and more particularly to the stabilization of such mixtures by addition of reaction products of salicylic aldehyde and certain aliphatic polyamines.

Hexachloroacetone is finding substantial use as a highly eilective herbicide. In such use it is advantageous to employ the hexachloroacetone in admixture with a hydrocarbon oil as diluent. Due to the low surface tension and high wetting ability of the hydrocarbon oil, the mixture has improved spreading and penetration powers. Among particularly suitable hydrocarbon oils are the so-called high aromatic herbicidal oils. These oils, obtained from petroleum cracking, contain at least about 35 weight percent of aromatics, at least about 50 Weight percent of total aromatics and olefins, and boil in the range of about 275 to 700 F. 7

Typical inspection of Chapman HB, a commercial high aromatic petroleum oil, is as follows:

Viscosity (SSU/ 100 F.) Pour point F.) l

We have found that hexachloroacetone varies greatly in stability when mixed with hydrocarbon oils. Parafiinic oils, kerosenes, diesel oils, etc., give mixtures of good stability. However, when a high aromatic petroleum oil containing olefins is employed, the resulting mixture, upon standing or in storage, is unstable, resulting in formation of objectionable sludge and evolution of hydrogen chloride with consequent loss of toxicant (hexachloroacetone) strength. Besides reducing toxicant strength, the evolved hydrogen chloride is extremely corrosive and detrimentally builds up pressure in closed containers.

In preparing hexachloroacetone for herbicidal use, the hexachloroacetone is formulated as a concentrate in hydrocarbon oil. The concentrate is then diluted several timeswith additional oil in the field for use as spray.

In formulating the hexachloroacetone, and particularly for dilution in'the field, it is'desirable to employthe convenient and inexpensive 'high aromatic petroleum oils. These herbicidal compositions are described in U.S.P. 2,764,479 of Everett E. Gilbert, which issued on September 25, 1956.

An object of the present invention is to retard the deterioration of hexachloroacetone in high aromatic petroleum oils containing olefins. Another object is to stabilize mixtures of hexachloroacetone and high aromatic petroleum oils containing olefins with reaction products of salicylic aldehyde and certain aliphatic polyamines. A further object is to provide new stabilized compositions of matter. Still further objects and advantages will appear hereinafter. I

3,043,674 Patented July 10, 1962 ice The above objects may be accomplished in accordance with our invention by incorporating in the mixture of hexachloroacetone and high aromatic petroleum oil contain-' ing olefins a stabilizing amount of the reaction'product of salicylic aldehyde and an aliphatic polyamine containing two primary amino groups.

The salicylic aldehyde-aliphatic polyamine reaction product is obtained in conventional manner by'condensing one mol of the polyamine with about two mols of salicylic aldehyde. Among the suitable polyamines which may be used are diethylenetriamine, triethylenetetramine,

converting hexachloroacetone into pentachloroacetone or some derivative thereof with concomitant release of hydrogen chloride.

Many different types of stabilizers, including antioxidants and chelating agents, were tested in an effort to re-' tard the deterioration of hexachloroacetone in high aromatic petroleum oils containing olefins but proved to be unsatisfactory. In view. of these results, it was indeed surprising when applicants discovered that incorporation of reaction products of salicylic aldehyde and polyamines containing two primary amino groups efiectively stabilized the hexachloroacetone-oil mixtures.

Small amounts of the reaction product of salicylic aldehyde and aliphatic polyamine have been found to successfully stabilize the hexachloroacetone-oil mixtures. Generally, the reaction product is used in amount ranging from about 0.01 to 1%, and preferably from about 0.01 to 0.25%, by weight of the hexachloroacetone plus oil. For most eflicient stabilization the amount tends to increase with increases in the proportion of hexachloroacetone in the mixture.

To determine the efiectiveness of the reaction products of salicylic aldehyde and aliphatic polyamines containing two primary amino groups, stability was tested in accord- .ance with the following procedure.

181 grams of a mixture of hexachloroacetone (30% by weight) and Chapman HB oil by weight), 5 clean six-penny nails and 0.023 gram (0.0125% by weight of the hexachloroacetone plus oil) of salicylic.

at the rate of about 5 bubbles per second by passing a slow stream of air into the inlet of the heating flask.

At the end of '12 hours, the contents of the hydrogen chloride absorption flask are titrated with 0.1 N NaOH using methyl red indicator to determine the milliequiv-' alents of hydrogen chloride evolved. The percent apparchloroaeetone.

Percent Millie- Stabltier quivalents,

5 acetone 1 V 2., 3 7. 0 3,3 2. 3 7. o a 2. 8 10. 1

{The original herachloroacetone contained 1.3% apparent pentafIhe testssettforth. in .following Table II were carried out .in the'mamier described above, 'using disalicylal-propanediar'riine 'l ,Z'tdstabiliz'e mixtures of hexachloro'acetone per tit). Thesede'sts tended to indicate that at least abo t. .0.0l% by weight of stabilizer was required for effective results.

Table II 2 fitabilizer -We e cen t pa HexachloroentPentachlor'o- Milliequivaacetone -acet0ne lentS'HGl Chapm I HB"-oil 05 100 217 1. 5 0.050 ;2.7 2.7 0.025 3.0 2.0 0.013 3.0 3.0 0.006 3.9 7.3 None 8.5 "39.0

".The' original hexachloroacetone contained 1.4% apparent pentachloroaeetone.

in none of the testsbf Tables I and' IIwas any visible slndge iorniation noted. 7 V

-Whil'e we havedisclosed the preferred embodiments of our invention, "it willibe apparent to those skilled' in the aft manyvariationsand-modifications may be made theie n 'deparfing rrom the spirit of our invention.

solely by are append d 'laims, l construed as broadly as permissiblefin'view-of flae priorart.

claim: p

. 1.*Aherbicidal-'composition-'compfising (l) 'a'mixture cciiitainiiig olefins au'd (2) an amountiof'the reaction remier of "salicylic aldehyde and an aliphatic p'olyamine sleeted' froin thelgroupconsisting' 6f "diethylenetriamine,

afiiiiie';1;5 I1iari1ino n=pentane, 1';6-'dia.niirio-n-hexane, l, lo diamino-n-decahe, 1*,2-diaminopropane; 1.7-diamino-nheptane, 1;4-diamino-n-bf1tane,- diaminoneopentane, 1,3- diarriinopropane, 3 ;3'-iminobispropylamine -and -l*,3-diaminopropanol-Z sufficient to retard deterioration of the hexeterramine; "tetraethyleriepentaniine, ethylenedi- I diamine 1,10 sufiicient to retard deterioration of the hexachloroacetone, said amount bein'gat least about 0.01%

achloroacetone, said amount being at least about 0.01% g by weight of the hexachloroacetone plus oil.

2. A herbicidal composition comprising (1) a mixture of hexachloroacetone and a high aromatic petroleum oil containing olefins and (2) an amount of disalicylidinetriethylenetetramine suflicient to retard deterioration of the hexachloroacetone, said amount being at least about 0.01% by weight of the hexachloroacetone plus oil.

3. A herbicidal composition comprising (1) a mixture of .hexachloroacetone and a high aromatic petroleum oil containing olefins and (2) an amount of disalicylidinetetraethylenepentarninesufiicientto retard deterioration of the hexachloroacetoue, said amount being at least about 0.01% by weight of the hexachloroacetoneplus oil.

4. A herbicidal composition comprising (1) a mixture of hexachloroacetone and a high aromatic petroleum oil containing olefins and (2) an amount of disalicylal heptanediamine 1,7 suflicient to retard deterioration of the hexachloroacetone, said amount being at least about 0.01% by weight of the hexachloroacetone plus oil.

5. A herbicidal composition comprising (1) a mixture of-hexachloroacetone and a high aromatic petroleum oil containing olefins and (2) anamount of vdisalicylal-pentadiamine 1,5 sufiicient to retard deterioration of .the hexa- -chloroacetone, said amount being at least about 0.01%

by weight of the hexachloroacetone plus oil.

6. A herbicidal composition comprising (1 a mixture of hexachloroacetone and a high aromatic petroleum oil containing olefins and (2) an amount of disalicylal-decaneby weight of the hexachloroacetone plus oil.

7. Themethod' of retarding deterioration of hexachloroacetone in a herbicidal mixture'of hexachloroacetoneand a high aromatic petroleum oil containing olefins which comprises incorporating insaid mixture a small amount of the reaction product of salicylicaldehyde and an'aliphatic 'pjolyamine selected fromthe group consisting of diethylenetriamine, 'triethylenetetramine, tctraethylenepentamine, ethylen'ediamine, 'l,'5-'diamino-n-pentane, 1 -,'6-

diamino-n-h'exane, "Ll'O-diaminom-"decane, 1,2-diaminopropane, 1,7'-diamino=n-h'eptane, 1,4'-diamino-n-butane,-di-

acetone in a herbicidal mixture .of' hexachloroacetone and The lscope of eu nvenaqn is, thereforefto belimited of hexachloroacetone and a high aromatic petroleum oil aminoneopentane, 1,'3=diaminopropane, 3';3'-iminobispropylamine and '1,'3-*diaminopropanol-2, said amount be -ing at least about 0.01% by weight of the hexachloroacetone plus oil.

8. The method of retarding deterioration of'hexachloroacetone in a herbicidal mixture of'hexachloroacetone and a high :aromatic petroleum oil containing zolefin's which comprises incorporating in said mixture a small amount of disalicylidinetriethylenetetramine, said amount being at least about 0.01% by weight of the hexachloroacetone plus oil.

9. The method of retarding deterioration of hexachloroahigh aromatic petroleum oil containing olefins which comprises incorporating in "said mixture a small amount of disalicylidine-tetraethylenepentamine, 'said' amount :being 'at least about'0l0l% by weight 'of'the hexachloroacetone plus oil.

10. The method of retarding "deteriorationof hexach-loroacetone in a'lherbicidal mixture of 'hexa'chloroacetone and 'a' high aromatic petroleum oil "containing olefins which comprises incorporating in said 'imixtui'e a man amount of disalicylal-heptanediamine 1,7, saidamdunt' being at least about 0.01% by wei'ghrtof thehexachloroacetone plus oil. w

'11. The method of retarding deterioration of hexach'loroacetone in a herbicidal mixture of hexachloroacetone and a high aromatic petroleum oil containing olefins which comprises incorporating in said mixturea small amount of disalicylal=pentanediamine1,5, said amount being 'at least about 0.01%" by weight of the" hexachloroac'etone plus oil.

5 '12. The method of retarding deterioration of hexachloroacetone in a herbicidal mixture of hexachloroacetone and a high aromatic petroleum oil containing olefins which comprises incorporating in said mixture a small amount of disalicylal-decanediaminc 1,10, said amount being at least about 0.01% by weight of the hexachloroacetone plus oil.

References Cited in the file of this patent NITED STATES PATENTS Downing et a1 Nov. 28, 1939 Thompson Nov. 1, 1949 Gilbert Sept. 25, 1956 Clough Feb. 3, 1959 

1. A HERBICIDAL COMPOSITION COMPRISING (1) A MIXTURE OF HEXACHLOROACETONE AND A HIGH AROMATIC PETROLELUM OIL CONTAINING OLEFFINSS AND (2) AN AMOUNT OF THE REACTION PRODDUCT OF SALICYLIC ALDEHYDE AN AN ALIPHATIC POLYAMINE SELECTED FROM THE GROUP CONSISTING OF DIETHYLLENETRIAMINE, TRIETHYLENETETRAMINE, TETRAETHLENEPENTAMINE, ETHYLENEDIAMINE, 1,5-DIAMINO-N-PENTANE, 1,6-DIAMINO-N-HEXANE, 1, 10-DIAMINO-NDECABNE, 1,2-DIAMINOPSROPANE, 1,7-DIAMINO-NHSEPTANE, 1,4-DIAMINO-N-BUTANE, DDIAMINONEPENTANE, 1,3DIAMINOPROPANE, 3,3-IMINOBISPRROPYLAMINE AND 1,3-DIAMACHLOROACETONE, SAID AMOUNT BEING AT LEASTL ABOUT 0.01% BY WEIGHT OF THE HEXACHLOROACETONE PLUS OIL. 